三维多孔结构和亲锌性梯度协同构筑无枝晶锌电极

doi:10.6023/A24010019

摘要/Abstract

锌离子电池具有能量密度高、安全性好、价格低廉等优点, 被认为是规模化储能的理想选择之一. 然而, 其锌负极在电化学循环过程中易产生枝晶、析氢和表面钝化等, 造成电池库伦效率低、锌利用率低和循环寿命短等缺陷, 限制了其规模化应用. 本工作采用电沉积法在自制三维多孔铜内先沉积具有高亲锌性的PbSn合金层, 再沉积Zn层, 最后通过化学置换, 在上层孔表面获得PbSn合金层, 其在ZnSO₄电解液中形成较低亲锌性的PbSO₄层, 最终形成由三维多孔内部到外部亲锌性逐渐降低的具有三维亲锌性梯度的锌电极3D Cu@PbSn@Zn@PbSn (3D Cu@PSZPS). 三维多孔结构可提高电极比表面积, 提供更均匀的电场分布, 降低电流密度, 提高锌沉积容量, 抑制枝晶生长、析氢和钝化; 内层孔PbSn合金具有高亲锌性, 可诱导锌从内层孔沉积, 抑制锌枝晶生长; Pb和Sn具有高析氢过电位, 可抑制析氢, 同时抑制由于析氢致使电极表面pH值升高而产生的钝化. 因此该电极结构可获得优异的电化学性能, 在电流密度5 mA•cm^-2, 面积容量1 mAh•cm^-2的条件下, 可实现锌的稳定沉积/剥离900次以上, 首圈成核过电位仅16.4 mV, 首圈库伦效率高达99.66%; 以此电极组装的对称电池可以稳定循环超过700 h; 采用商业MnO₂与之匹配得到的MnO₂||3D Cu@PSZPS全电池在0.3 A•g^-1时具有238.7 mAh•g^-1的可逆比容量和300次循环后79.4%的容量保持率, 在1.8 A•g^-1的电流密度下可稳定循环2000次以上.

关键词: 水系锌离子电池, 负极, 协同策略, 三维多孔, 亲锌性梯度

Zn-ion batteries have been considered as one of the most promising grid storage devices due to their high energy densities, high safety, and low cost. However, the Zn anode suffers dendrite growth, hydrogen evolution and surface passivation, resulting in low coulombic efficiency, low Zn utilization, and poor cyclability. In this work, PbSn alloy is firstly electrodeposited in the self-prepared three-dimensional (3D) porous Cu, then a Zn layer is electrodeposited on it, finally the partial Zn layer on outer pores is replaced by PbSn alloy, which will transform into PbSO₄ in ZnSO₄-based electrolyte, and a Zn electrode with 3D porous structure and zincophile gradient is achieved 3D Cu@PbSn@Zn@PbSn (3D Cu@PSZPS). The 3D porous structure can provide high specific area, small and uniform current distribution, as a result enhance Zn plating capacity, inhibit Zn dendrites growth, hydrogen evolution and passivation. The PbSn alloy layer in inner pores can induce Zn plating from inner to outer pores, inhibit dendrites growth; high hydrogen evolution overpotential feature of Pb and Sn can inhibit hydrogen evolution, and also inhibit the passivation caused by increase of pH value. This modification strategy effectively circumvents the inherent limitations associated with solely relying on a single strategy. Therefore, this electrode demonstrates excellent electrochemical performance. It can stably cycle for more than 900 times at 5 mA•cm^-2, 1 mAh•cm^-2 with a high first coulombic efficiency of 99.66%, low first nucleation potential of 16.4 mV. The symmetrical cell assembled using this electrode can stably cycle for more than 700 h. The MnO₂||3D Cu@PSZPS full cell shows a high reversible specific capacity of 238.7 mAh•g^-1 at 0.3 A•g^-1 and a capacity retention of 79.4% over 300 cycles, and can be stably cycling more than 2000 times under the current density of 1.8 A•g^-1.

Key words: aqueous zinc-ion battery, anode, cooperative strategy, three-dimensional porous, zincophile gradient

引用此文

宋瑞, 赵铭钦, 王帅, 卢垚, 鲍晓冰, 罗巧梅, 苟蕾, 樊小勇, 李东林. 三维多孔结构和亲锌性梯度协同构筑无枝晶锌电极[J]. 化学学报, 2024, 82(4): 426-434.

Rui Song, Mingqin Zhao, Shuai Wang, Yao Lu, Xiaobing Bao, Qiaomei Luo, Lei Gou, Xiaoyong Fan, Donglin Li. Three-Dimensional Porous Structure and Zincophile Gradient Enabling Dendrite Free Zinc Anode[J]. Acta Chimica Sinica, 2024, 82(4): 426-434.

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图/表 5

图1. (a) 3D Cu@PbSn (3D Cu@PS), 3D Cu@PbSnZn (3D Cu@PSZ), 3D Cu@PbSnZnPbSn (3D Cu@PSZPS)电极的制备流程示意图, (b) 3D Cu@PSZPS电极的改性原理示意图

Figure 1. (a) Schematic diagram of the preparation processes of 3D Cu@PbSn, 3D Cu@PbSnZn, 3D Cu@PbSnZnPbSn electrodes, (b) Schematic diagram of the modification principle of 3D Cu@PSZPS electrode

图2. (a) 2D Zn, (b) 3D Cu, (c) 3D Cu@Zn, (d) 3D Cu@PS, (e, f) 3D Cu@PSZPS的扫描电镜图像, 3D Cu@PSZPS电极上(g) Zn, (h) Sn, (i) Pb和(j) O元素的EDS能谱图像, 3D Cu@PSZPS电极上(k) Zn, (l) Pb和(m) Sn元素的XPS谱图

Figure 2. SEM images of (a) 2D Zn, (b) 3D Cu, (c) 3D Cu@Zn, (d) 3D Cu@PS, (e, f) 3D Cu@PSZPS, EDS mapping images of (g) Zn, (h) Sn, (i) Pb and (j) O distribution on 3D Cu@PSZPS, XPS spectra of (k) Zn, (l) Pb and (m) Sn on 3D Cu@PSZPS

图3. 半电池的(a) 库伦效率, (b) 首圈成核过电位, (c) Zn在2D Cu, 3D Cu和3D Cu@PS电极上的沉积过电位, (d) 2D Zn, 3D Cu@Zn和3D Cu@PSZPS电极的析氢过电位, (e) 塔菲尔曲线, (f) 由塔菲尔曲线计算所得的腐蚀电压和腐蚀电流, (g) 2D Zn, (h) 3D Cu@Zn, (i, j) 3D Cu@PSZPS在电解液中浸泡72 h的扫描电镜图像, 3D Cu@PSZPS电极浸泡后(k) Zn, (l) Sn, (m) Pb和(n) S元素的EDS能谱图像, 3D Cu@PSZPS电极浸泡后(o) Zn, (p) Pb和(q) Sn的XPS谱图

Figure 3. (a) Coulombic efficiency, (b) first nucleation overpotential of half-cells, (c) Zn deposition overpotential on the 2D Cu, 3D Cu and 3D Cu@PS, (d) hydrogen evolution overpotentials of 2D Zn, 3D Cu@Zn and 3D Cu@PSZPS; (e) Tafel profiles and (f) corresponding self-corrosion potentials and currents calculated from Tafel profiles; SEM images of (g) 2D Zn, (h) 3D Cu@Zn, (i, j) 3D Cu@PSZPS after soaking for 72 h, EDS mapping images of (k) Zn, (l) Sn, (m) Pb, and (n) S distribution on 3D Cu@PSZPS and XPS spectra of (o) Zn, (p) Pb and (q) Sn on 3D Cu@PSZPS after immersion experiment

图4. 2D Zn, 3D Cu@Zn和3D Cu@PSZPS对称电池在(a) 1 mA?cm-2/0.5 mAh?cm-2, (b) 5 mA?cm-2/0.5 mAh?cm-2电流条件下的时间电压曲线, (c) 不同电流密度下的极化对比; (d) 2D Zn, (e) 3D Cu@Zn和(f) 3D Cu@PSZPS电极循环后的扫描电镜图像, (g) Zn, (h) Sn和(i) Pb元素的EDS能谱图像

Figure 4. Voltage-time curves of symmetric cells using 2D Zn, 3D Cu@Zn and 3D Cu@PSZPS cycled at (a) 1 mA?cm-2/0.5 mAh?cm-2, (b) 5 mA?cm-2/0.5 mAh?cm-2, (c) polarization comparison at different current densities; SEM images of (d) 2D Zn, (e) 3D Cu@Zn and (f) 3D Cu@PSZPS after cycling, EDS mapping images of (g) Zn, (h) Sn and (i) Pb distribution on 3D Cu@PSZPS

图5. 0.3 A?g-1电流条件下(a) 全电池的循环性能, (b) 2D Zn||MnO2, (c) 3D Cu@Zn||MnO2和(d) 3D Cu@PSZPS||MnO2的容量电压曲线. (e) 0.15, 0.3, 0.6, 1.8, 3, 6 A?g-1电流条件下的全电池倍率性能, (f) 2D Zn||MnO2, (g) 3D Cu@Zn||MnO2和(h) 3D Cu@PSZPS||MnO2在相应电流条件下的容量电压曲线

Figure 5. (a) Cyclability of full cell, and capacity-voltage profiles of (b) 2D Zn||MnO2, (c) 3D Cu@Zn||MnO2 and (d) 3D Cu@PSZPS||MnO2 at 0.3 A?g-1. (e) Rate performance at 0.15, 0.3, 0.6, 1.8, 3, 6 A?g-1, and corresponding capacity-voltage profiles of (f) 2D Zn||MnO2, (g) 3D Cu@Zn||MnO2 and (h) 3D Cu@PSZPS||MnO2

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